Nitric acid manufacture



NOV- 8, 1938. R. s. RICHARDSON NITRIC ACID MANUFACTURE Filed Aug. 29, 1934 INVENTOR.

z/m ww ATTORNEY,

Patented Nov. 8, 1.938

UNITED STATES PATENT OFFICE NITRIC Aem MANUFACTURE Ralph S. Richardson, Scarsdale, N. Y., assignor to Chemical Construction Corporation, a corporation of Delaware Application August 29,

6 Claims.

are well known. It will be seen. from the above equation that it is one which is not favored by high pressures; on the contrary the reaction equilibrium is more favorable at relatively low pressures than at higher ones.

Most of the processes now in use for obtaining nitric acid from the gaseous products of this reaction involve, in general, the successive steps of cooling the gases, permitting the NO to oxidize to NO2 either by the excess oxygen contained in the gases or by the addition of oxygen, and the final step of absorbing the oxidized gases in van 25 aqueous absorbing medium such as water or dilute nitric acid. The reactions involved in these steps are as follows:

v and it willbe seen that these are both reactions, the equilibrium of which is favored by increased pressure since they take place with diminution of volume.

It is now standard practice to carry out the above series of reactions in a system operating under atmospheric pressure, only suicient draft being used to force the gases through the apparatus. 'This method of operation results in a highly favorable equilibrium of reaction 1 above, but the pressure conditions are not the, most favorable for reactions 2 and 3 and it is diflicult to obtain acid of a concentration higher than 50% from the remaining two reactions without the use of refrigeration or other artificial temperature control. v 4 It has also been proposed to operate the entire system under a considerable pressure, in order to obtain a. more favorable equilibrium for reactions 2 and 3 and a product acid of increased concentration. It must be noted, however, thatthe increased eiciency in the absorp-l tion end of the system takes place only with a corresponding displacement of equilibrium in the ammonia oxidation reaction, and the incomplete 1934-, serial No. '141,984 (o1. 23,-162) conversion lowers the ,strength of the acid produced by a corresponding amount,'besides representing a loss of efficiency and a source of impurity in the product. n I

In view of the disadvantages in the ordinary 5 pressure systems, it has recently been proposed to use superatmospheric pressures only in the absorption end of the system, that is to say, to carry out the ammonia oxidation at atmospheric or subatmospheric pressure followed by compresl0l sion of the nitric oxide gases and absorption under pressures higher than atmospheric. While from a theoretical standpoint the conditions so obtained are favorable to the various reactions,

from a practical standpoint of plant construction 1 `is only slightly displaced to the left by a rst moderate increase of pressure above atmospheric and that the loss of efficiency represented by an increase of pressure of approximately 1 to 2 atmospheres, i. e., an operating pressure of approximately 2 to 3 atmospheres absolute, is prac- A3o L tically compensated by the corresponding decrease inthe undesirable side reaction:

A comparison of the equilibria and optimum conditions of these two reactions shows that there is a super-atmospheric pressure range of from 1 to approximately 3 atmospheres withi-n which the e'ciency of the ammonia oxidation, expressed in moles NO obtained per mole of ammonia in- 40 troduced, is well within the permissible conversion efciency for plantsl of this type. Above pressures of approximately 3 atmospheres, or 45 pounds per square inch absolute, the equilibrium of reaction 1 becomes unfavorably displaced, 45 so that operation above this point represents a loss in eicie-ncy of the entire plant. An object of the present invention, therefore, is the provision of a superatmospheric system for the production of nitric acid involving only such a preliminary compression of gases in the ammonia oxidation stage that the reaction is not unfavorably affected thereby.

A further object is the subsequent compression of the oxidized gases to pressures suitable for absorption with the production o! a nitric acid i product of relatively high concentration.

A' final object includes apparatus for the production of nitric acid by oxidation of ammoniacontaining gases under relatively low superatmospheric pressuresl followed by absorption in an aqueous absorbing medium at higher pressures. Further objects of the invention will be in part made apparent from the following description vand in' part pointed out in the .appended claims.

'I'he invention will be further illustrated by reference to the accompanying drawing, which is a diagrammatic representation of a nitric acid plant construction in accordance with the principles thereof. In this drawing, the ilrst stages of the system are represented in the conventional manner by circles, including the customary preheater for the ammonia-air mixture, the ammonia oxidizer in which the preheated mixture is passedover a platinum gauze catalyst 'at temperatures of SOO-900 C., the tail gas heater and waste heat boiler for utilizing the -excess heat of` the nitric oxide gases coming from the converter, and the preheater referred to in which -these gases are passed in heat exchanging relation with the incoming gases. y

The ammonia and air are admitted to the system through vaived pipes I and 2 and pass to the compressor 3, which is of a design and construction suitable for compressing the gases to 2 to 3 atmospheres absolute pressure. From the compressor the gases pass along the course shown by the arrows, andipreferably leave the preheater at a temperature of approximately 250 C. The gases then pass through pipe 4 into the condenser 5 which, as shown, is of relatively large size and is capable of such rapid cooling that the water produced by oxidation oi.' the ammonia is con'- densed and removed before the NO in the gases Vhas had time to oxidize to NO: and be absorbed in the condensate.

The rapidity of cooling is primarily desirable to produce more concentrated NO: gases for the absorber. Since the weak acid drip from the condenser may be used for irrigating the absorber, a/sillustrated in the drawing, the question is nferely one of the strength of the product y acid desired and not one of loss of oxides of nitrogen from the system.

Preferably this condenser is of such a type that the condensate r'uns counter-current to the gases, so that it leaves as weak nitric acid at equilibrium with the gases entering the condenser. The condenser shown is one of the tubular type, conacid, a small chromium steel compressor may be provided, to raise the total pressure to an absorption range of 4 to 'I atmospheres absolute, and preferably to an operating range of approximately 5 atmospheres.

Since this compressor must do only a relatively smaller part of the worlv. required of compressors located at this point in the prior system above referred to and since due to prior 'compression the actual volume of gases entering the compressor is smaller, its size and installation cost are correspondingly decreased.

The -gases from f' the condenser are passed through the pipe I8, to a compressor 20 which may be constructed of chrome steel. While this compressor is preferably of a size and construction to compress the gases from their rst stage pressure to an absorbing pressure of 4 to 6 atmospheres, which is suitable for the production of an acid of 60 to 65% concentration with ordinary cooling water, it is understood that higher pressures may be employed in the absorption stage if desired. For example, a compressor may be used, preferably provided with a cooling Jacket and means for further cooling the gases after compression. which willv compress the oxides of nitrogen to such an extent that they may be directly condensed as liquid N204, which is suitable for reacting with oxygen and water under pressure to produce nitric acid of any desired strength. Pressures up to 30'atmospheres absolute have been used for this purpose, and are included in the present invention.

From the compressor, the gases now pass through pipe 2i to an oxidizer 22, in which the reaction 2NO+O2=2NO1 is brought to completion. By reason of the'increased pressure this reaction takes place at greater speed than in the ordinary atmospheric plants. The amount of acid drip formed is less than in prior processes becauseof the greater removal of water in the primary condensers due to the gas being under pressure. It is to be {inderstood that the term absorbing system is intended to include an absorber either with or without an intermediate oxidizer or cooler, as volume must always be allowed for oxidation of NO to NO2 either as an oxidizer or else in the base of the absorption tower. In any case, gases leaving compressor 20 must be cooled to remove heat of compression and to obtain the lower tempera- ,tures where oxidation is more rapid. By admitting additional air or oxygen to the oxidizer as at slsting of an outer shell 6 with top and bottom 3l, it is possible to operate with a correspondingly pieces 1 and 8 and tube sheets 9 and`| forming gas exit and entrance compartments II and I2. Between the tube sheets are mounted gas tubes I3, and around these tubes are placed horizontal baiiles I4, to provide an extendedl travel over the tubes for the cooling water which enV ters at I5 and leaves at I6.` The weak acid collected as condensate runs 0E through the pipe I1 and is collectedin storage tank I8, from which it may be pumped to the absorbers if desired.

The gases leaving the exit compartment II of the condenser are at' approximately the temperature of the cooling water used, which is about 20 C., and are saturated with water at this temperature under the pressure employed. At this point, there are several alternative procedures which may-be adopted, depending upon the type and size of the plant and the product desired. In a plant operating to produce a 60 to 65% nitric decreased excess of air in the ammonia oxidizer,v

which decreases the rate of oxidation of NO during the cooling stage.

The gases leaving the oxidizer are passed through pipe 24 into the base of the absorbing tower 25, through which they rise counter to a ow of an aqueous absorbing medium such as water or dilute nitric acid which is admitted at the top through pipe 26. Concentrated nitric acid `so produced is collected from the base of the tower through pipe 21 and is run to storage tank 2U, while the tail gases are vented from the system through exit pipe 29 provided with relief valve 30. In commercial practice these tail gases, instead of being vented, are frequently passed to a ytail gas heater placed in the system directly after the ammonia oxidizer, as indicated in the drawing, and are then expanded in an expansion engine in order to utilize the energy which they contain. 'Ihis expansion engine is used to drive the compressors 3 and 20, or for any other purpose where work -is required, and this practice may be followed in the operation of ,the present invention if desired.

From the above, it will be apparent that a nitric acid system has been designed which gives at least the eiliciency of one in which the ammonia oxidation takes place at atmospheric pressure followed by compression and absorption under pressures greater than atmospheric, while maintaining the lower plant cost of an all pressure system. This is highly desirable.

While the invention has been shown and described with reference to particular embodiments, yet, obviously, I do not wish to be limited thereto, but the invention is to be construed broadly and restricted only by the scope of the claims.

I claim:

l. A process of producing nitric acid which comprises compressing ammonia and oxygen containing gases to pressures substantially above atmospheric but not substantially greater than 45 pounds per square inch absolute, bringing about oxidation in the gases at these pressures to produce gases containing nitric oxide, and both oxidizing said nitric oxide to higher oxides of nitrogen and absorbing said oxides of nitrogen from the reacted gases in an aqueous absorbing medium under pressures substantially greater than those employed in the oxidation step.

2. A process of producing nitric acid which comprises compressing ammonia and oxygen containing gases to pressures substantially above atmospheric but not substantially greater than 45 pounds per square inch absolute, bringing about oxidation in the gases at these pressures to produce gases containing nitric oxide, and both oxidizing said nitric oxide to higher oxides of nitrogen and absorbing said oxides of nitrogen from the reacted gases in an aqueous absorbing medium under pressures greater than 60 pounds per square inch absolute.

3. A process of producing nitric acid which comprises compressing --1 2f onia and oxygen containing gases to pressures substantially above atm'jospheric but not substantially greater than 45 peunds per square inch absolute, bringing about omdation in the gases at these pressures and at elevated temperatures to produce hot gases containing nitric oxide, cooling the reacted gases to condense water therefrom, and both oxidizing said nitric oxide to higher oxides of nitrogen and absorbing said oxides of nitrogen from the reacted gases in an aqueous `absorbing medium under pressures substantially greater than those employed in the oxidation step.

4. A process -of producing nitric acid which comprises compressing ammonia and oxygen containing gases to pressures substantially above atmospheric but not substantially greaterthan 45 pounds per square inch absolute, bringing about oxidation in the gases at these pressures and at elevated temperatures to produce hot gases containing nitric oxide, cooling the reacted gases at these pressures to condense a major part of the water therefrom, compressing to a still higher pressure, and oxidizing said nitric oxide` to higher oxides of nitrogen and absorbing said oxides of nitrogen from the gases in an aqueous absorbing medium under said higher pressure.

5. A process of producing nitric acid which comprises compressing ammonia and oxygen containing gases to pressures substantially above atmospheric but not substantially greater than 45 pounds per square inch absolute, bringing about oxidation in the gases at these pressures and at elevated temperatures to produce hot gases containing nitric oxide, quickly cooling the reacted gases at these pressures to condense a major part of the water 'therefrom vwhile passving the condensate counter to the hot gases,

compressing the gases'to a still higher pressure, and then oxidizing said nitric oxide to higher ozdes of nitrogen and absorbing said oxides of nitrogen from the reacted gases in an aqueous absorbing medium under said higher pressure.

` 6. A nitric acid plant comprising in combination a plurality of gascompressors for ultimately attaining a pressure oi' at least 4 atmospheres absolute, an ammonia oxidizer, a' condenser, an oxidizer, andan absorbing system'for contacting gaseous oxides of nitrogen with an aqueous absorbing medimin, the irst gas compressor being located ahead of the ammonia oxidizer and being operative to produce a pressure substantially above atmospheric but not substantially greater than 45 pounds per square inch absolute, and at least one subsequent gas compressor beinglocated subsequent to the ammonia oxidizer and being operative to compress the oxidized gases to a still higher pressure, said subsequent gas compressor being fabricated from an alloy of iron which is` resistant to corrosion byl moist oxides of nitrogen.

RALPH 8. RICHARDSON. 

